CN107651852A - The seal glass and its preparation and application mixed outside a kind of cobalt sesquioxide nickel oxide - Google Patents
The seal glass and its preparation and application mixed outside a kind of cobalt sesquioxide nickel oxide Download PDFInfo
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- CN107651852A CN107651852A CN201710940272.3A CN201710940272A CN107651852A CN 107651852 A CN107651852 A CN 107651852A CN 201710940272 A CN201710940272 A CN 201710940272A CN 107651852 A CN107651852 A CN 107651852A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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Abstract
The invention discloses a kind of Co2O3The seal glass and its preparation and application mixed outside NiO, glass powder raw material composition is M2O、MeO、SiO2、Al2O3, (M=Li, Na, K；Me=Ca, Mg, Sr), mass ratio is 20 ~ 40%, 0 ~ 20%, 40 ~ 60%, 0 ~ 20%.The Co mixed outside2O3NiO quality is the 0 ~ 30% of glass powder.Pass through the Co mixed outside2O3Partly enter with NiO in glass network, play synergy, reduce interface energy, improve sealing property；Co2O3It can promote to form fine and close spinel layer in seal interface, effectively prevent the elements diffusion of seal interface, suppress the interfacial reaction between glassy metal.Unnecessary outer powder of mixing also improves the overall thermal coefficient of expansion of seal, sealing materials, reduces the coefficient of thermal expansion mismatch with metal base, effectively reduces the stress of seal interface.
Description
Technical field
The invention belongs to the glass sealing field of metal base, and in particular to a kind of Co2O3The seal glass mixed outside-NiO and
Its preparation and application.
Background technology
Solid fuel cell（SOFC）It is the regenerative resource electrochemical apparatus to receive much attention in recent years, its high efficiency, nothing
Pollution, structure of whole solid state and the extensive adaptability to pluralities of fuel gas are widely used it.SOFC technologies are future source of energy knots
The key technology of allosteric transformation, there is the advantage that chemical energy directly efficiently, can be changed into contamination-freely to electric energy.With solid fuel
The fast development of the other assemblies of battery compares, and seal, sealing materials turn into the bottleneck for restricting its development.Glass material is due to it
Distinctive performance turns into the first choice of seal, sealing materials.At present, domestic and international researcher is mainly adjusted by glass ingredient and control heat
The measures such as reason system improve the sealing property of glass.However, the coefficient of thermal expansion mismatch between seal, sealing materials and base material causes
Seal interface upper stress concentrate so that sealing-in failure can not still avoid.
The content of the invention
In order to solve the above problems, the invention provides a kind of Co2O3 The seal glass mixed outside-NiO and its preparation and make
With method, pass through the Co mixed outside2O3 Enter with NiO parts in glass network, synergy can not only be played, reduce interface
Can, significantly improve sealing property；And Co2O3It can promote to form fine and close spinel layer in seal interface, effectively prevent sealing-in
The elements diffusion at interface, suppress the interfacial reaction between metal-glass.Unnecessary outer powder of mixing also improves seal, sealing materials entirety
Thermal coefficient of expansion, the coefficient of thermal expansion mismatch with metal base is reduced, effectively reduce the stress of seal interface.Raw material letter of the present invention
Singly it is easy to get, cost is low, and technique is simple, feasible, has reached practical and industrialized condition.
The present invention is implemented by following technical solution：
A kind of Co2O3The seal glass mixed outside-NiO, the Co of its quality 0 ~ 30% is mixed in glass powder2O3Powder is mixed outside-NiO
Material；The raw material composition of the glass powder is M2O、MeO、SiO2、Al2O3, (M=Li, Na or K；Me=Ca, Mg or Sr), matter
It is 20 ~ 40%, 0 ~ 20%, 40 ~ 60%, 0 ~ 20% to measure fraction, and above material quality fraction sum is 100%.
Prepare Co as described above2O3The method for the seal glass mixed outside-NiO comprises the following steps：
（1）The raw material of glass powder is well mixed；Founded by 900-1500 DEG C, soaking time 1-4 hours；To what is melted
Glass metal, chilling is carried out, obtain glass frit；Then, glass frit is crushed, grinding or ball milling, glass is obtained after sieving
Powder；
（2）Glass powder is mixed powder, dispersant and solvent and be mixed into slurry with outer, above metallic plate, is carried out certain
Heat treatment, obtain sealing-in idiosome.
The step（2）Outer powder of mixing be Co2O3With one or more of mixtures in NiO.
The step（2）Dispersant for methylcellulose, epoxy resin, polyvinyl butyral resin, fish oil, polypropylene
One or more of mixtures in acid, polyvinyl alcohol and polyacrylamide.
The step（2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene and acetone in one kind or
Several mixtures.
Idiosome, which is placed in, needs sealing-in position, is heated up in electric furnace with 1-5 DEG C/min speed, 300-400 DEG C of insulation
0.5-2 hours, 550-700 DEG C of processing 0.5-2 hour is then warming up to 1-5 DEG C/min speed.
The remarkable advantage of the present invention is：
（1）The Co mixed outside2O3Enter with NiO parts in glass network, synergy can not only be played, reduce interface energy, show
Write and improve sealing property；
（2）Mix Co outside2O3Addition can promote to be formed the spinel layer of densification in seal interface, effectively prevent seal interface
Elements diffusion, suppress the interfacial reaction between metal-glass;
（3）Unnecessary outer powder of mixing also improves the overall thermal coefficient of expansion of seal, sealing materials, reduces the thermal expansion with metal base
CTE mismatch, effectively reduce the stress of seal interface;
(4) preparing raw material that the present invention selects is cheap, process stabilizing, has reached practical and industrialized condition.
Embodiment
A kind of Co2O3The seal glass mixed outside-NiO, the Co of its quality 0 ~ 30% is mixed in glass powder2O3Mixed outside-NiO
Powder；The raw material composition of the glass powder is M2O、MeO、SiO2、Al2O3, (M=Li, Na or K；Me=Ca, Mg or Sr),
Mass fraction is 20 ~ 40%, 0 ~ 20%, 40 ~ 60%, 0 ~ 20%, and above material quality fraction sum is 100%.
Prepare Co as described above2O3The method for the seal glass mixed outside-NiO comprises the following steps：
（1）The raw material of glass powder is well mixed；Founded by 900-1500 DEG C, soaking time 1-4 hours；To what is melted
Glass metal, chilling is carried out, obtain glass frit；Then, glass frit is crushed, grinding or ball milling, glass is obtained after sieving
Powder；
（2）Glass powder is mixed powder, dispersant and solvent and be mixed into slurry with outer, above metallic plate, is carried out certain
Heat treatment, obtain sealing-in idiosome.
The step（2）Outer powder of mixing be Co2O3With one or more of mixtures in NiO.
The step（2）Dispersant for methylcellulose, epoxy resin, polyvinyl butyral resin, fish oil, polypropylene
One or more of mixtures in acid, polyvinyl alcohol and polyacrylamide.
The step（2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene and acetone in one kind or
Several mixtures.
Idiosome, which is placed in, needs sealing-in position, is heated up in electric furnace with 1-5 DEG C/min speed, 300-400 DEG C of insulation
0.5-2 hours, 550-700 DEG C of processing 0.5-2 hour is then warming up to 1-5 DEG C/min speed.
Table 1 is the sealing glass composition table in embodiment 1-4（Quality compares percentage）
Embodiment 1：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 1 in table 1, a certain amount of analysis pure raw material is weighed（Al2O3、SiO2、Na2O、
CaO）, it is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the sky of chamber type electric resistance furnace
In gas atmosphere, 1300 DEG C are heated to 3 DEG C/min, is incubated 1 hour；Then, crucible is taken out, melt is poured into anxious in deionized water
It is cold, dry the fragment for obtaining glass melt；Grinding, 100 mesh sieves are crossed, obtain glass powder, added outside a certain amount of and mix analysis
Pure powder.By mixed powder and polyvinyl alcohol, fish oil, ethanol and toluene（Weight ratio is followed successively by 80%, 2%, 1%, 10%, 7%）Mixing
Into slurry, ball milling disperses in ball mill；Flow casting molding, spontaneously dry, be then cut into the idiosome of required shape；By embryo
Body, which is placed in, needs sealing-in position, is heated up in electric furnace with 2 DEG C/min speed, and 1 hour is incubated at 400 DEG C, then with 2 DEG C/
Min speed is warming up to 600 DEG C and handled 2 hours.The example is to preferably constitute.The stainless steel that melt after insulation is poured into after preheating
In grinding tool, Φ=10mm, d=25mm glass cylinder, with 10 DEG C/min's on NETZSCH DIL 402EP thermal dilatometers are obtained
The rate of heat addition is tested, and obtains the linear expansion coefficient of glass.Co2O3Addition with NiO is that the linear expansion coefficient of 2% glass is
1.31×10-5/K.Pull open method test and show that the interface binding power of the glass coating and battery material is 39MPa.
Embodiment 2：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 2 in table 1, a certain amount of analysis pure raw material is weighed（Al2O3、SiO2、Na2O、
CaO）, it is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the sky of chamber type electric resistance furnace
In gas atmosphere, 1350 DEG C are heated to 3 DEG C/min, is incubated 1 hour；Then, crucible is taken out, melt is poured into anxious in deionized water
It is cold, dry the fragment for obtaining glass melt；Grinding, 100 mesh sieves are crossed, obtain glass powder, added outside a certain amount of and mix analysis
Pure powder.By mixed powder and methylcellulose, polyvinyl alcohol, n-butanol and acetone（Weight ratio is followed successively by 82%, 2%, 2%, 8%,
6%）Slurry is mixed into, ball milling disperses in ball mill；Flow casting molding, spontaneously dry, be then cut into the embryo of required shape
Body；Idiosome, which is placed in, needs sealing-in position, is heated up in electric furnace with 2 DEG C/min speed, and 1 hour is incubated at 380 DEG C, then with
2 DEG C/min speed is warming up to 620 DEG C and handled 1 hour.The example is to preferably constitute.Melt after insulation is poured into after preheating not
Become rusty steel grinding tool in, obtain Φ=10mm, d=25mm glass cylinder, on NETZSCH DIL 402EP thermal dilatometers with 10 DEG C/
Min rate of heat addition test, obtain the linear expansion coefficient of glass.Co2O3Addition with NiO is the line expansion of 5% glass
Coefficient is 1.37 × 10-5/K.Pull open method test and show that the interface binding power of the glass coating and battery material is 42MPa.
Embodiment 3：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 3 in table 1, a certain amount of analysis pure raw material is weighed（Al2O3、SiO2、Na2O、
CaO）, it is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the sky of chamber type electric resistance furnace
In gas atmosphere, 1400 DEG C are heated to 3 DEG C/min, is incubated 1 hour；Then, crucible is taken out, melt is poured into anxious in deionized water
It is cold, dry the fragment for obtaining glass melt；Grinding, 100 mesh sieves are crossed, obtain glass powder, added outside a certain amount of and mix analysis
Pure powder.By mixed powder and epoxy resin, polyacrylamide, isopropanol and toluene（Weight ratio is followed successively by 84%, 1.5%,
0.5%、9%、5%）Slurry is mixed into, ball milling disperses in ball mill；Flow casting molding, spontaneously dry, be then cut into required
The idiosome of shape；Idiosome, which is placed in, needs sealing-in position, is heated up in electric furnace with 2 DEG C/min speed, small in 360 DEG C of insulations 1
When, then it is warming up to 640 DEG C with 2 DEG C/min speed and handles 1 hour.The example is to preferably constitute.Melt after insulation is poured into
In stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass cylinder, in NETZSCH DIL 402EP thermal dilatometers are obtained
On tested with the 10 DEG C/min rate of heat addition, obtain the linear expansion coefficient of glass.Co2O3Addition with NiO is 10% glass
The linear expansion coefficient of glass is 1.44 × 10-5/K.Pull open method test and show that the interface binding power of the glass coating and battery material is
45MPa。
Embodiment 4：The preparation and sealing-in of material
According to the proportioning of each component of embodiment 4 in table 1, a certain amount of analysis pure raw material is weighed（Al2O3、SiO2、Na2O、
CaO）, it is well mixed within 24 hours with planetary ball mill ball milling；Then powder is put into platinum crucible, is placed in the sky of chamber type electric resistance furnace
In gas atmosphere, 1450 DEG C are heated to 3 DEG C/min, is incubated 1 hour；Then, crucible is taken out, melt is poured into anxious in deionized water
It is cold, dry the fragment for obtaining glass melt；Grinding, 100 mesh sieves are crossed, obtain glass powder, added outside a certain amount of and mix analysis
Pure powder.By mixed powder and polyvinyl butyral resin, polyacrylic acid, isopropanol and acetone（Weight ratio is followed successively by 83%, 2%,
1%、9%、5%）Slurry is mixed into, ball milling disperses in ball mill；Flow casting molding, spontaneously dry, be then cut into required shape
The idiosome of shape；Idiosome, which is placed in, needs sealing-in position, is heated up in electric furnace with 2 DEG C/min speed, small in 340 DEG C of insulations 1
When, then it is warming up to 660 DEG C with 2 DEG C/min speed and handles 1 hour.The example is to preferably constitute.Melt after insulation is poured into
In stainless steel grinding tool after preheating, Φ=10mm, d=25mm glass cylinder, in NETZSCH DIL 402EP thermal dilatometers are obtained
On tested with the 10 DEG C/min rate of heat addition, obtain the linear expansion coefficient of glass.Co2O3Addition with NiO is 15% glass
The linear expansion coefficient of glass is 1.30 × 10-5/K.Pull open method test and show that the interface binding power of the glass coating and battery material is
40MPa。
The present invention obtains the glass that can implement sealing-in in low temperature by above-mentioned implementation.Its significant effect embodies a concentrated reflection of glass
In terms of glass seal and excellent interface binding power good in cement.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (7)
- A kind of 1. Co2O3The seal glass mixed outside-NiO, it is characterised in that：Its quality 0 ~ 30% is mixed in glass powder Co2O3Powder is mixed outside-NiO；The raw material composition of the glass powder is M2O、MeO、SiO2、Al2O3, wherein M=Li, Na, K；Me =Ca, Mg, Sr, mass fraction are 20 ~ 40%, 0 ~ 20%, 40 ~ 60%, 0 ~ 20%, and above material quality fraction sum is 100%.
- 2. Co according to claim 12O3The seal glass mixed outside-NiO, it is characterised in that：It is mixed in glass powder The Co of quality 4 ~ 30%2O3Powder is mixed outside-NiO；The raw material composition of the glass powder is M2O、MeO、SiO2、Al2O3, wherein M= Li, Na, K；Me=Ca, Mg, Sr, mass fraction be 25 ~ 40%, 0 ~ 15%, 45 ~ 60%, 0 ~ 15%, above material quality fraction it With for 100%.
- 3. one kind prepares Co as claimed in claim 1 or 22O3The method for the seal glass mixed outside-NiO, it is characterised in that：Bag Include following steps：（1）The raw material of glass powder is well mixed；Founded by 900-1500 DEG C, soaking time 1-4 hours；To what is melted Glass metal, chilling is carried out, obtain glass frit；Then, glass frit is crushed, grinding or ball milling, glass is obtained after sieving Powder；（2）Glass powder is mixed powder, dispersant and solvent and be mixed into slurry with outer.
- 4. Co according to claim 32O3The preparation method for the seal glass mixed outside-NiO, it is characterised in that：The step （2）Outer powder of mixing be Co2O3With one or more of mixtures in NiO.
- 5. Co according to claim 32O3The preparation method for the seal glass mixed outside-NiO, it is characterised in that：The step （2）Dispersant for methylcellulose, epoxy resin, polyvinyl butyral resin, fish oil, polyacrylic acid, polyvinyl alcohol and poly- third One or more of mixtures in acrylamide.
- 6. Co according to claim 32O3The preparation method for the seal glass mixed outside-NiO, it is characterised in that：The step （2）Solvent be water, ethanol, isopropanol, n-butanol, toluene, dimethylbenzene and acetone in one or more of mixtures.
- A kind of 7. Co as claimed in claim 12O3The application method for the seal glass mixed outside-NiO, it is characterised in that：By slurry Being positioned over needs the position of sealing-in, is heated up in electric furnace with 1-5 DEG C/min speed, 300-400 DEG C of insulation 0.5-2 hour, so 550-700 DEG C of processing 0.5-2 hour is warming up to 1-5 DEG C/min speed afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710940272.3A CN107651852B (en) | 2017-10-11 | 2017-10-11 | Cobaltous oxide-nickel oxide externally-doped sealing glass and preparation and use methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710940272.3A CN107651852B (en) | 2017-10-11 | 2017-10-11 | Cobaltous oxide-nickel oxide externally-doped sealing glass and preparation and use methods thereof |
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| Publication Number | Publication Date |
|---|---|
| CN107651852A true CN107651852A (en) | 2018-02-02 |
| CN107651852B CN107651852B (en) | 2020-08-11 |
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| CN201710940272.3A Active CN107651852B (en) | 2017-10-11 | 2017-10-11 | Cobaltous oxide-nickel oxide externally-doped sealing glass and preparation and use methods thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046606A (en) * | 2018-02-13 | 2018-05-18 | 福州大学 | A kind of nitrogen oxides seal glass of phosphate containing chromium and preparation method thereof |
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| CN1116612A (en) * | 1994-09-10 | 1996-02-14 | 电子工业部第十二研究所 | Glass solder for sealing and its preparing method |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN106277794A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Glass-glass composite seal and its preparation method and application |
| CN106746673A (en) * | 2016-11-24 | 2017-05-31 | 福州大学 | Anti-corrosion glass and its preparation and application that a kind of Co Ni are co-doped with |
| WO2017122578A1 (en) * | 2016-01-12 | 2017-07-20 | 日本電気硝子株式会社 | Sealing material |
-
2017
- 2017-10-11 CN CN201710940272.3A patent/CN107651852B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116612A (en) * | 1994-09-10 | 1996-02-14 | 电子工业部第十二研究所 | Glass solder for sealing and its preparing method |
| CN102503136A (en) * | 2011-11-14 | 2012-06-20 | 中国科学院上海硅酸盐研究所 | Sealing material for medium/low-temperature solid oxide fuel battery and preparation method thereof |
| CN106277794A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Glass-glass composite seal and its preparation method and application |
| WO2017122578A1 (en) * | 2016-01-12 | 2017-07-20 | 日本電気硝子株式会社 | Sealing material |
| CN106746673A (en) * | 2016-11-24 | 2017-05-31 | 福州大学 | Anti-corrosion glass and its preparation and application that a kind of Co Ni are co-doped with |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046606A (en) * | 2018-02-13 | 2018-05-18 | 福州大学 | A kind of nitrogen oxides seal glass of phosphate containing chromium and preparation method thereof |
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| CN107651852B (en) | 2020-08-11 |
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